METHOD OF KILLING FUNGI, YEAST OR BACTERIA WITH SELECTED MONOCYCLIC MONOTERPENES

Abstract: Method of killing bacteria, fungi, or yeast by treating them with lethal concentrations of an agent selected from the group of carveol, dihydrocarveol, dihydrocarvone, menth-1-en-9-ol, and limonen-10-ol.

Description: METHOD OF KILLING FUNGI, YEAST OR BACTERIA WITH SELECTED MONOCYCLTC MONOTERPENES TECHNICAL FIELD This invention relates to a method of using selected monocyclig monoterpenes as microbicides for fungi, yeats, or bacteria. BACKGROUND OF THE INVENTION (1) Field of the Invention During the study of limonene as a hand cleaner, the applicant found that limonene can be made bactericidal and fungicidal as was demonstrated in U.S. Patent Nos. 5,153,229 and 5,229,425. A review of the literature revealed that oxygenated limonene contains several oxida¬ tion products including: limonene-l,2-oxide, limonene-8, 9-oxide, l-menthene-9-al, a-2, 8-p-menthadiene-l-ol, B-2, 8-p-menthadiene-l-ol, dihydrocarvone, B-cymenol, carvone, cis-carveol, and trans-carveol, as was outlined by Bain in U.S. Patent 2,863,882 and 3,014,047. Blumann listed the compounds formed by the auto-oxidation of limonene in Chemical Abstracts, Volume 63, 1965, on page 1819, which included cis and trans-carveol, trans-p-menth-8-ene-l,2-diol, limonene 1,2-epoxide, limonene 8, 9-epoxide, cis and trans- p-mentha-2,8-dien-l-ol, and perillyl alcohol. The applicant found that lethal concentrations of carveol, dihydrocarvone, and dihydrocarveol are excellent ANTI-YEAST and ANTI-FUNGAL antimicrobials that kill yeast and fungi, while limonene-10- ol and menth-l-en-9-ol in lethal concentrations, are excel¬ lent antimicrobials that kill bacteria, yeast, and fungi. Carveol, dihydrocarveol, dihydrocarvone, limonene-lO-ol, and menth-l-en-9-ol are monocyclic monoterpene with the following chemical formulae: Carveol Dihydrocarveol Dihydrocarvone Limonen-10-ol Menth-1-en-9-ol Carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol, and menth-l-en-9-ol are oils that can be emulsified in water. Each has either a terpenic, spearmint, or fruity aroma, is soluble in alcohol and is miscible in corn oil, olive oil, and soybean oil. They are all insoluble in water and glycerine. Carveol, dihydrocarveol, and dihydrocarvone have been used as bactericides, but heretofore, they have never been shown to kill yeast nor fungi. Limonen-10-ol and menth-1-en-9- ol have never been recognized as bactericides, fungicides, nor anti-yeast antimicrobials. Carveol can be produced by the oxidation of limonene as was outlined by Bain in US Patents 2,863,882 and 3,014,047. Carveol can be obtained from A-pinene, and B-pinene by the Cu+ catalyzed oxidation with benzoyl peroxide as was demonstrated by Walling et al in Canadian Patent 981,695. Mestroni et al showed that carveol can be produced by the catalyzed conversion of carvone and dihydrocarvone to carveol as was outlined in German Offen 3,008,671 in the Chemical Abstracts, Volume 93, 1980, page 807. Bain, in US Patent 2,803,647 showed his method of producing carveol and dihydrocarveol and their esters. In the Indian Journal of Chemistry, 1975, 13(11), pages 1239-40, Mistra outlined a method of producing carveol and dihydrocarveol from piperitone. Leffingwell (in US Patent 3,538,164) produced dihydrocarveol from limonene-1,2-epoxide by the addition of small amounts of perchloric acid. As described by Khanna, Vijay and Ladwa, P.H. in the Indian Journal of Chemistry, Section B 1987, 26B (9), 816-822, menth-l-en-9-ol can be produced by the hydroboration - oxidation of carvone. Limonen-10-ol is available commercially from the Aldrich Chemical Company, 940 Saint Paul Avenue, Milwaukee, Wisconsin 53233, catalogue number 21,841-3, and can be obtained from Professor George Majetich PhD, Department of Chemistry, University of Georgia, Athens, Georgia 30602. It is produced by a proprietary method of oxygenating d-limonene. (2) Description of the Prior Art Zukerman studied the effect of auto-oxidized limonene on bacteria and found it was weakly bacteriostatic, was unstable, and lost its bacteriostatic effect on keeping as was discussed in Nature 168: 517 (1951) . He never studied the antimicrobial activity of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol, menth-l-en-9-ol, nor purposefully oxidized limonene. Kurita investigated the fungicidal activity of several components of essential oils in Biol. Chem.. 45(4), 945-952, 1981, and found that cineole, anethole, safrole, d-limonene, a-pinene, b-pinene, camphene, b-myrcene, caryophyllene, b-cymene, d- camphor, benzaldehyde, vanillin, and furfural are NOT FUNGICIDAL while cinnamaldehyde, phenol, perillyl aldehyde, citral, perillyl alcohol, geraniol, citronellol, 1-nonanol, 1-deconal, 1- menthol and borneol have minimal to good fungicidal activity depending on the compound tested. He never studied the ANTI-BACTERIAL, ANTI-YEAST, nor the ANTI-FUNGAL activity of limonen-10-ol nor menth-l-en-9-ol and never studied the ANTI-YEAST nor the ANTI-FUNGAL activity of carveol, dihydrocarveol, nor dihydrocarvone. Peter Tetenyi et al studied the essential oils obtained from twelve different specimens of Tanacetum vulqare L. and found eight of the twelve oil specimens to be bactericidal in a concentration of 100 ug/ml against 85-90% of nineteen different bacteria tested, and 100% fungicidal in a concentration of 50 ug/ml against sixteen species of fungi tested. He delineated numerous chemical components in the oils, but he never studied any of those individual components to determine which, if any, had anti-bacterial, anti-yeast, and/or anti-fungal activity as was outlined in Herba Hungarica, 1981, Tom 20, No. 1- 2, pages 57-74. In the Botanical Gazette 122, 194-8 (1961), R.C. French showed that carveol stimulates (rather than inhibits) the germination of wheat stem rust uredospores suggesting that carveol promotes the growth of fungi. Knoblock found that the antimicrobial action of essential oils is related to their ability to penetrate the cell membrane of bacteria and fungi as was shown in the Journal of Essential Oil Res. 1989, 1(3), 119-28, but he never demonstrated which components of the essential oils, if any, have anti¬ bacterial, anti-yeast and/or anti-fungal activity. Chastain and Sanders made limonene bactericidal and fungicidal by oxidation as was outlined in U.S. Patents 5,153,229, and 5,229,425 but they never studied carveol, dihydrocarveol, nor dihydrocarvone for anti-yeast nor anti-fungal activity and never studied limonen-10-ol nor menth-l-en-9-ol for anti-bacterial, anti-yeast, nor anti-fungal activity. Gauvreau showed a means of producing disinfecting compositions in US Patent 3,595,975 by combining cetyl pyridinium with terpenes to form antiseptics. Gauvreau never studied the use of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol nor menth-l-en-9-ol alone nor in combination with cetyl pyridinium. A. Morel revealed the sterilizing action of carveol, dihydrocarveol, and their ozonization products in Comp_. Rend. Soc. Biol. Volume 115, pages 536-8 (1934) . He demonstrated the bactericidal activity of carveol and dihydrocarveol, but he never studied carveol, dihydrocarveol nor dihydrocarvone for anti-yeast nor anti-fungal activity and never studied limonene-10-ol and menth-1-en-ol for anti¬ bacterial, anti-yeast nor anti-fungal activity. J.C. Maruzzella and L. Liguori reported the in vitro anti-fungal activity of essential oils in the Journal of the American Pharmaceutical Association, Vol. XLVII, No. 4, April 1958, pages 250-4, but they did not study the anti-yeast nor the anti-fungal activity of carveol, dihydrocarveol, nor dihydrocarvone, and never studied the anti-bacterial, anti-yeast nor anti- fungal activity of limonene-10-ol nor menth-1-en- 9-ol. J.C. Maruzzella and Jerry Baiter showed the action of essential oils on phytopathogenic fungi in the Plant Disease Reporter Vol. 43, No. 11, Nov. 1959, pages 1143-1147, but they did not study the anti-yeast nor the anti-fungal activity of carveol, dihydrocarveol, nor dihydrocarvone and they never studied the anti-bacterial, anti-yeast nor the anti-fungal activity of limonene-10-ol nor menth-1-en-ol. D.D. Whitehead in US Patent 3,743,747 showed the fungicidal activity of several oxo-derivatives of limonene and dipentene, but he never studied the fungicidal activity of carveol, dihydrocarveol, dihydrocarvone, limonene- lO-ol, nor menth-1-en-ol. J.C. Maruzzella et al reported the action of odoriferous organic chemicals and essential oils on wood-destroying fungi in the Plant Disease Reporter, Vol 44, No. 10 (1960) ; carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol, and menth-l-en-9- ol were not studied. Murdock and Allen showed the germicidal effect of sodium benzoate against yeast is enhanced by orange peel oil and d-limonene (stripper oil) , as was reported in Food Technology, Vol 14, No. 9, 1960, pages 441-5. They never studied the action of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol, nor menth-l-en-9-ol against bacteria, yeast nor fungi. Kellner et al studied ethereal oils for antimicrobial activity, but they never studied any of the chemical constituents in the oils for anti¬ bacterial, anti-yeast nor anti-fungal activity as was outlined in Arneimittel-Forsch 5, 224-9 (1955) . Carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol, and menth-l-en-9-ol were not studied for anti-bacterial, anti-yeast, and anti- fungal activity. It should be pointed out that the drugs which are bactericidal are usually not fungicidal, and drugs which are fungicidal are usually not bactericidal. In humans, the use of bactericidal antibiotics frequently promote the growth of yeast. Table A, which follows, exemplifies the anti-bacterial, anti-yeast and anti-fungal activity of several commonly used anti-bacterial, anti-yeast, and anti-fungal antibiotics. TABLE A ANTIBIOTICS ANTIBIOTIC ACTIVITY AGAINST A.ANTIBACTERIAL Gm + Bac Gm' Bac AFBact Yeast Fungi 1. Ampicillin YES YES NO NO NO 2. Cephalothin YES YES NO NO NO 3. Chloram- YES YES NO NO NO phenicol 4. Erythromycin YES NO NO NO NO 5. Ethambutol NO NO YES NO NO 6. Gentamicin YES YES NO NO NO 7. Isoniazid NO NO YES NO NO 8. Nitro- furantoin NO YES NO NO NO 9. Penicillin YES NO NO NO NO 10. Rifampin YES NO YES NO NO 11. Streptomycin YES YES YES NO NO 12. Sulfonamides NO YES NO NO NO 13. Tetracycline YES YES NO NO NO 14. Vancomycin YES YES NO NO NO B. ANTIYEAST 1. Nystatin NO NO NO YES NO 2. Gentian NO YES NO violet ANTIFUNGAL 1. Chlotri- mazole NO NO NO YES YES 2. Griseofulvin NO NO NO NO YES Gm + Bac = Gram Positive Bacteria, Gm " Bac = Gram Negative Bacteria, AFBac = Acid Fast Bacteria, YES = Kills Organism, NO = No Activity Against Organism -li¬ lt should be noted in the table above that none of the anti-bacterial antibiotics kill yeast nor fungi, and none of the anti-yeast nor anti- fungal antibiotics kill bacteria. Thus an anti- fungal or anti-yeast antibiotic is not expected to kill bacteria, and an anti-bacterial antibiotic is not expected to kill yeast nor fungi. Anti-fungal antibiotics do not necessarily kill yeast, and anti-yeast antibiotics do not necessarily kill fungi. Several significant differences between yeast and fungi are known and are listed. For instance: (1) a yeast culture can be grown in 24- 48 hours while a fungus culture requires 7-14 days to grow. (2) Yeast readily grow on blood agar while fungi grow on sabouraud dextrose agar. (3) In humans, the use of anti-bacterial antibiotics promotes the growth of yeast but not fungi. (4) Several anti-yeast antibiotics do not kill fungi and several anti-fungal antibiotics do not kill yeast. DISCLOSURE OF THE INVENTION This invention relates to the use of carveol, dihydrocarveol, and dihydrocarvone to kill yeast and fungi, and to the use of limonene-10-ol and menth-l-en-9-ol to kill bacteria, yeast, and fungi. Carveol, dihydrocarveol, and dihydrocarvone are oils that are available commercially. They are recognized to have bactericidal activity, but heretofore, they have not been recognized to have anti-yeast nor anti- fungal activity. Limonene-10-ol and menth-1-en-ol are available commercially. They have never been recognized to have bactericidal, fungicidal nor anti-yeast activity. Carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol, and menth-l-en-9-ol are slightly viscous, and when applied, readily adhere to glass, metal, wood, cloth, rope, book covers, paper, cement, ceramics, paint, plastic, plant surfaces, skin, mucus membranes, and teeth leaving an oily film. They are not soluble in water but they adhere to surfaces that allows prolonged exposure and makes them ideal for treating infections of plants, animals, and humans. The exact method of killing bacteria, yeast and fungi is unknown, but it is thought that carveol, dihydrocarveol, dihydrocarvone, limonene- lO-ol and menth-l-en-9-ol kill bacteria, yeast, and fungi by lysing the cell membrane of the organism which is lethal to the organisms. In practice, any surface on which it is desirable to kill or prevent the growth of yeast is treated by swabbing, wiping, painting, washing, brushing, spraying, or any other direct application technique with effective concentrations of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol or menth-l-en-9-ol to kill yeast, while fungicidal concentrations of carveol, dihydrocarveol, dihydrocarvone, limonene- lO-ol or menth-l-en-9-ol kill or prevent the growth of fungi, and bactericidal concentrations of limonene-10-ol or menth-l-en-9-ol kill or prevent the growth of bacteria. Alternatively, carveol, dihydrocarveol, or dihydrocarvone can be incorporated in creams, ointments, tinctures, gels, suppositories, paints, sealers, sprays, aerosols, tampons, toothpastes, solutions, emulsions, soaps, scrubs, mouthwashes, or antiseptics and applied anywhere it is desirable to kill or prevent the growth of yeast or fungi. Limonene-10-ol and menth-l-en-9-ol can be incorporated in creams, ointments, tinctures, gels, suppositories, paints, sealers, sprays, aerosols, tampons, toothpastes, solutions, emulsions, soaps, scrubs, mouthwashes, or antiseptics and applied anywhere it is desirable to kill or prevent the growth of bacteria, yeast, or fungi. BEST MODE FOR CARRYING OUT THE INVENTION The following examples are illustrative of the best mode for carrying out the invention. They are, obviously, not to be construed as limitative of the invention since various other embodiments can readily be evolved in view of the teachings provided herein. EXAMPLE 1 ANTI-YEAST AND FUNGICIDAL ACTIVITY OF dl-CARVEOL, DIHYDROCARVEOL AND DIHYDROCARVONE, AND THE BACTERICIDAL, ANTI-YEAST, AND THE FUNGICIDAL ACTIVITY OF LIMONEN-10-OL AND MENTH-1-EN-9-0L The anti-yeast and the anti-fungal compounds contemplated by this invention are carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol and menth-l-en-9-ol which were studied for anti-yeast and anti-fungal activity against the organisms: Candida albicans, the yeast that causes infections of skin and mucus membranes; the cutaneous fungus Microsporum canis, that cause skin infections in man and animals; and the mildew causing fungi Aureobasidium pullulans OM 279C, Cladosporium cladosporiodes OM 489, and Phialophora licmicola OM 5922. The minimal effective concentration of carveol, dihydrocarveol, dihydrocarvone, limonen- lO-ol and menth-l-en-9-ol that kill yeast and the fungicidal concentration of carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol, and menth-l-en-9-ol that kill fungi are listed in Table B below. The bactericides contemplated by this invention are limonen-10-ol and menth-l-en-9-ol which were studied for bactericidal activity. The bacteria tested included: Staphylococcus aureus ATCC 25923, Streptococcus mutans which causes dental plaque, Escherichera coli 7, Salmonella 14 (para B) , Pseudomonas aeriσinosa 115. The carveol, dihydrocarveol, dihydrocarvone, and menth-l-en-9-ol used in these tests were obtained from Aldrich Chemical Company, 940 Saint Paul Avenue, Milwaukee, Wisconsin 53201. The Catalogue Number and Lot Number for each were carveol - 19,238-4 and PX03504EV, dihydrocarveol - 21,842-1 and 09516DZEZ, dihydrocarvone - 21,828-6 and EY00305HW, and menth-l-en-9-ol 18,374-1 and 01130DTAW & 01130DTEZ respectively. The limonene- 10-ol used in these tests was obtained from George Majetich PhD, Department of Chemistry, University of Georgia, Athens, Georgia 30602, was 99.9% pure by gas chromatography, and its structure was confirmed by NMR mass spectroscopy. Limonen-10-ol can be obtained from the Aldrich Chemical Company, Catalogue Number 21,841-3. TABLE B ANTI-YEAST AND FUNGICIDAL ACTIVITY OF dl CARVEOL, DIHYDROCARVEOL, DIHYDROCARVONE, LIMONEN-10-OL AND MENTH-1-EN-9-0L AND BACTERICIDAL ACTIVITY OF LIMONEN-10-OL AND MENTH-1-EN-9-0L CARVEOL ORGANISM MINIMUM EFFECTIVE CONCENTRATION 10 MIN 60 MIN 24 HOURS A. YEAST 1. Candida albicans 0.06 0.02 0.005 B. FUNGI MINIMUM FUNGICIDAL CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Microsporum canis 0.01 0.01 0.01 2. Aureobasidium pullulans Om 279C 0.02 0.02 0.01 3. Cladosporium cladosporiodes OM 489 0.06 0.01 0.01 4. Phialophora licmicola OM 5922 0.01 0.01 0.01 DIHYDROCARVEOL ORGANISM MINIMUM EFFECTIVE CONCENTRATION 10 MIN 60 MIN 24 HOURS A. YEAST 1. Candida albicans 0.06 0.06 0.01 MINIMUM FUNGICIDAL CONCENTRATION A. FUNGI 10 MIN 60 MIN 24 HOURS 1. Microsporum canis 0.01 0.02 0.01 2. Aureobasidium pullulans Om 279C 0.02 0.02 0.01 3. Cladosporium cladosporiodes OM 489 0.01 0.01 0.01 4. Phialophora liσnicola OM 5922 0.01 0.01 0.01 DIHYDROCARVONE ORGANISM MINIMUM EFFECTIVE CONCENTRATION 10 MIN 60 MIN 24 HOURS A. YEAST 1. Candida albicans >0.016 0.016 0.005 B. FUNGI MINIMUM FUNGICIDAL CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Microsporum canis >0.16 >0.16 0.0012 2. Aureobasidium pullulans Om 279C >0.16 0.06 0.0012 3. Cladosporium cladosporiodes OM 489 >0.16 0.16 0.0012 4. Phialophora liσnicola OM 5922 0.16 0.10 0.0012 LIMONEN-10-OL ORGANISM MINIMAL BACTERICIDAL CONCENTRATION A. BACTERIA 10 MIN 60 MIN 24 HOURS 1. Staphylococcus aureus, ATCC 25923 0.06 0.01 0.005 2. Streptococcus mutans 0.02 0.01 0.005 3. Escherichera coli 7 0.01 0.005 0.005 4. Salmonellal4 (para B) 0.005 0.005 0.005 5. Pseudomonas aeruαinosa ATCC 115 <0.2 <0.2 <0.2 B. YEAST MINIMUM EFFECTIVE CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Candida albicans 0.01 0.02 0.005 C. FUNGI MINIMUM FUNGICIDAL CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Cladosporium cladosporides OM489 0.01 0.01 0.0025 2. Aureoblasidium pullans OM279C 0.005 0.0025 0.0025 MENTH-1-EN-9-OL ORGANISM MINIMAL BACTERICIDAL CONCENTRATION A. BACTERIA 10 MIN 60 MIN 24 HOURS 1.Staphylococcus aureus, ATCC 25923 0.06 0.06 0.0025 2. Streptococcus mutans 0.10 0.005 0.0012 3. Escherichera coli 7 0.06 0.005 0.005 4. Salmonellal4 (para B) 0.01 0.005 0.0025 5. Pseudomonas aeruσinosa ATCC 115 >0.5 >0.5 >0.5 MENTH- 1 -EN- 9 -0L B. YEAST MINIMUM EFFECTIVE CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Candida albicans 0.02 0.01 0.0025 C. FUNGI MINIMUM FUNGICIDAL CONCENTRATION 10 MIN 60 MIN 24 HOURS 1. Cladosporium cladosporides OM489 0.005 0.0025 0.0025 2. Aureoblasidium pullans OM279C 0.005 0.0025 0.0025 The standard assay used to test the activity of carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol and menth-l-en-9-ol against fungi was as follows: various dilutions of carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol and menth-l-en-9-ol were individually prepared in Sabouraud dextrose broth medium. An inoculum of 10 6 colony-forming units (CFU/ml) of fungi was introduced into each test, after which it was incubated at 37°C in air, and subcultured (0.01ml) at 10 minutes, 60 minutes, and 24 hours onto agar media free of carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol and menth-l-en-9-ol. Results were expressed as the minimal lethal concentration, i.e. the lowest concentration of carveol (ml carveol/total ml of test) , dihydrocarveol (ml dihydrocarveol/total ml of test) , dihydrocarveol (ml dihydrocarvone/total ml of test) , limonene-10-ol (ml limonene-10-ol/total ml of broth) or menth-l-en-9-ol (ml menth-l-en-9- ol/total ml of broth) with no detectable viable colonies following subculture onto media free of carveol, dihydrocarveol, dihydrocarvone, limonen- lO-ol and menth-l-en-9-ol. The standard assay used to test the activity of carveol, dihydrocarveol, dihydrocarvone, limonen-10-ol and menth-l-en-9-ol against yeast and limonene-10-ol and menth-l-en-9-ol against different strains of bacteria was as follows: various dilutions of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol and menth-l-en-9-ol were prepared in an appropriate broth medium for each test strain. An inoculum of 10 6 colony- forming units (CFU) /ml was used. Each test was incubated at the proper temperature for each organism and subcultured (0.01 ml) at 10 minutes, 60 minutes, and 24 hours onto agar media free of carveol, dihydrocarveol, dihydrocarvone, limonen- lO-ol and menth-l-en-9-ol. Results were expressed as the minimal lethal concentration, i.e. the lowest concentration of carveol (ml carveol/total ml of test) , dihydrocarveol (ml dihydrocarveol/total ml of test) , dihydrocarvone (ml dihydrocarvone/total ml test) , limonen-10-ol (ml limonen-10-ol/total ml of test) and menth-1- en-9-ol (ml menth-l-en-9-ol/total ml of test) killing at least 99.99% of the bacterial or yeast inoculum. Details of each assay are presented in Table C which follows. TABLE C Test conditions used to assay the anti-yeast and the fungicidal activity of carveol, dihydrocarveol, dihydrocarvone, limonene-10-ol and menth-l-en-9-ol and the bactericidal activity of limonene-10-ol and menth-l-en-9-ol are shown below. ORGANISM BROTH MEDIUM AGAR MEDIUM CONDITIONS 1. Yeast Sabouraud 5% sheep air at 37°C dextrose blood 2. Fungi Sabouraud Sabouraud air at 30°C dextrose dextrose agar 3. Bacteria Staphylo-, Mueller- 5% sheep Air at 37°C coccus Hinton blood Enterobac- teriacea, and Pseudomonas Strepto¬ Todd- 5% sheep 10% C0 2 in coccus Hewitt blood air at 37°C EXAMPLE 2 FORMULATIONS WHICH INCLUDE THE ANTI-YEAST AND FUNGICIDAL COMPOUNDS CARVEOL, DIHYDROCARVEOL, AND DIHYDROCARVONE AND THE BACTERICIDAL, ANTI-YEAST, FUNGICIDAL COMPOUNDS LIMONEN-10-OL AND MENTH-1-EN- 9-OL The following formulations are prepared using carveol, dihydrocarveol, dihydrocarvone, limonen- lO-ol and menth-l-en-9-ol in solutions, gels, soaps, paints, pastes, creams, ointments, suppositories, tampons, aerosols, and emulsions. When yeast or fungi are treated with carveol, dihydrocarveol, or dihydrocarvone containing formulations, the formulations kill or prevent the growth of yeast and fungi. When bacteria, yeast or fungi are treated with limonen-10-ol or menth- l-en-9-ol containing formulations, the formulations kill or prevent the growth of bacteria, yeast or fungi. A. LIQUIDS 1. SOLUTIONS OR SPRAYS CHEMICAL % OF TOTAL RANGE ACTION a. Limonen-10-ol 5.0% 0.1-50% bacteri- cide Corn Oil 95.0% 50-99.9% diluent 100.0% CHEMICAL % OF TOTAL RANGE ACTION b. Carveol 1.0% 0.1-50% fungi¬ cide Ethyl 99.0% 50-99.9% diluent Alcohol 100.0% 2. MOUTHWASH CHEMICAL % OF TOTAL RANGE ACTION a. Menth-1-en- 50.0% 0.1-50% anti- 9-ol yeast Flavor 2.0% 1-5% flavor Ethyl 48.0% 45-98.9% diluent Alcohol 100.0% B. DENTIFRICE 1. LIQUID CHEMICAL % OF TOTAL RANGE ACTION Liquid soap concentrate 5.0% 2-10% surfac¬ tant Saccharin 0.2% 0.1-1.0% flavor Clove Oil 1.0% 0.5-3.0% flavor Cinnamon Oil 0.5% 0.5-3.0% flavor Peppermint Oil 0.5% 0.5-3.0% flavor Ethyl Alcohol 42.6% :19.5-95.3% diluent Color 0.2% 0.1-0.5% color Menth-l-en-9-ol 50.0% 1-50% bacteri- 100.0% cide 2. GEL CHEMICAL % OF TOTAL RANGE ACTION Sodium ono- fluorophosphate 0.8% 0.5-1.5% anti- plaque Limonen-10-ol 50.0% 1-50% bacteri- cide Hydrated silica xerogel 10.0% 8-15% abrasive Hydrated thickening silica 8.5% 5-10% binder Sorbitol 70% solution 18.8% 5-73.3% humectant Polyethylene glycol 32 5.0% 3-7% bodying agent Sodium lauryl sulfate 1.5% 1-2% surfac¬ tant Carboxymethyl cellulose gum 1.0% 0.5-2% binder S D alcohol 1.0% 0 .5-2% stabi¬ lizer Flavor 3.0% 2-4% flavor Saccharin 0.2% 0 .1-0.5% flavor F D & C Green #3 0.1% 0 .1-0.5% color F D & C Yellow #10 0.1% 0 .1-0.5% color 100.0% 3. PASTE CHEMICAL % OF TOTAL RANGE ACTION Sodium mono- fluorophosphate 0.8% 0.5-1.5% anti- plaque Limonen-10-ol 50.0% 1-50% bacteri- cide Dicalcium phosphate dihydrate 22.0% 20.4-30% abrasive Water 16.0% 11.1-69.5% diluent Glycerine 5.1% 4.5-12.5% bodying agent Flavor 2.0% 2-3% flavor Sodium lauryl sulfate 1.5% 1-2% surfac¬ tant Carboxymethy1 cellulose gum 1.4% 0.5-2.0% binder Tetrasodium pyrophosphate 1.0% 0.5-2.0% binder Sodium saccharin 0.2% 0.1-0.5% flavor 100.0% C. OINTMENTS & SUPPOSITORIES WITH AND WITHOUT HYDROCORTISONE 1. OINTMENT WITH HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarveol 1.0% 0.1-15.0% fungi¬ cide Polyethylene glycol 3350 59.5% 48.5-59.7% bodying agent & emulsi- fier Polyethylene glycol 400 39.5% 31.5-39.7% bodying agent & emulsi- fier Hydrocortisone 1.0% 0.5-5.0% anti- 100.0% inflam¬ matory 2. OINTMENT WITHOUT HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarvone 1.0% 0.1-15.0% anti- yeast Polyethylene glycol 3350 59.5 51.0-59.95% bodying agent & e ulsi- fier Polyethylene glycol 400 39.5% 34.0-39.95% bodying 100.0% agent & emuls- ifier 3. SUPPOSITORY WITHOUT HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Limonen-10-ol 1.0% 0.1-15% bacteri- cide Polyethylene glycol 1000 9.5% 51.0-59.95% bodying agent & emulsi- fier Polyethylene glycol 3350 39.5% 34.0-39.95% bodying 100.0% agent & e ulsi- fier 4. SUPPOSITORY WITH HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarveol 1.0% 0.1-15% anti- yeast Polyethylene glycol 1000 74.0% 60.0-75.2% bodying agent & emulsi- fier Polyethylene glycol 3350 24.0% 20.0-24.2% bodying agent & e ulsi- fier Hydrocortisone 1.0% 0.5-5.0% anti- 100.0% inflam¬ matory D. CREAMS WITHOUT HYDROCORTISONE 1.CHEMICAL % OF TOTAL RANGE ACTION Carveol 1.0% 0.1-15.0% anti- yeast Cetyl alcohol 15.0% 12.0-18.0% thickener Arlacel 165 ** 5.0% 3.5-7.5% e ulsi- fier Sorbitol 70% solution 5.0% 3.5-8.0% humectant Water 74.5% 51.5-80.9% diluent 100.0% 2.CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarvone 1.0% 0.1-15.0% anti- yeast Spermaceti wax 12.5% 10.0-15.0% thickener Sorbitan monostearate Polyethylene 20 10.0% 7.5-12.5% emulsi- fier Sorbitan monostearate 6.0% 4.0-8.0% emulsi- fier Water 75.5% 49.5-78.4% diluent 100.0% E. CREAMS WITH HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Menth-l-en-9-ol 1.0% 0.1-15.0% anti- yeast Cetyl alcohol 15.0% 12.0-18.0% thicken Arlacel 165 ** 5.0% 3.5-7.5% emuls- ifier Sorbitol 70% solution 5.0% 3.5-8.0% humecta Hydrocortisone 1.0% 0.5-5.0% anti- infla - matory Water 73.0% 46.5-80.4% diluent 100.0% * Croda, Inc., 51 Madison Ave., New York, New York 10010 ** Glycerol monostearate and polyoxyethylene stearate ICI of America (Formerly Atlas Chemical Industries) , Wilmington, Delaware 19899 F. TAMPONS CHEMICAL % OF TOTAL RANGE ACTION Limonen-10-ol (2cc) 2Gm 8.0% 1-15% bacteri- cide Tampon 23Gm 92.0% 85-99% reservoir 100.0% for bac- tericide G. AEROSOLS WITHOUT HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarveol 5.0% 0.5-50% anti- yeast Ethyl alcohol 95.0% 50-99.5% diluent 100.0% Pressurized nitrogen propellant at 100-125 psig CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarvone 10.0% 0.5-50.0% anti- yeast Soybean Oil 90.0% 50.0-99.5% diluent 100.0% Pressurized nitrogen propellant at 100-125 psig H. AEROSOL WITH HYDROCORTISONE CHEMICAL % OF TOTAL RANGE ACTION Menth-l-en-9-ol 10.0% 0.5-50% bacteri- cide Soybean oil 98.0% 45-99.0% diluent Hydrocortisone 1.0% 0.5-5.0% anti- 100.0% inflam¬ matory Pressurized nitrogen propellant at 100-125 psig OIL IN WATER EMULSION CHEMICAL % OF TOTAL RANGE ACTION (1) Carveol 0.1% 0.1-50% anti- yeast (2) Corn oil 10.0% 10-15% oil (2) Arlacel 40** 2.0% 1-3% emulsi- fier (2) Tween 40 3.0% 2-4% emulsi- fier (3) Water 84.9% 28-86.9% diluent 100.0% Heat (2) to 70°C. Heat (3) to 72°C. Add (3) to (2) with continuous agitation. When (3) and (2) cool to 40°C, add (1) with continuous agitation until room temperature is reached. OIL IN WATER EMULSION WITH SOAP (FUNGICIDAL SOAP) CHEMICAL % OF TOTAL RANGE ACTION (1) Dihydrocarveol 1.0% 0.1-25% fungi¬ cide (2) Corn oil 30.0% 20.0-40.0% oil (2) Arlacel 40** 2.0% 1.0-3.0% emulsi- fier (2) Tween 40 3.0% 2.0-4.0% e ulsi- fier (2) Liquid soap concentrate 3.5% 2.5-5.0% surfac¬ tant (3) Water 60.5% 23-74.4% diluent 100.0% Heat (2) to 70°C. Heat (3) to 72°C. Add (3) to (2) with continuous agitation. When (3) and (2) cool to 40°C, add (1) with continuous agitation until room temperature is reached. K. WATER IN OIL EMULSION CHEMICAL % OF TOTAL RANGE ACTION (1) Limonen-10-ol 1.0% 0.1-25% anti- yeast (2) Arlacel 186** 3.0% 2.0-4.0% emulsi- fier (2) Soybean oil 15.0% 10.0-25.0% oil (2) Ceresin wax 0.5% 0.3-0.6% thickener (2) Beeswax 0.5% 0.3-0.6% thickener (2) Tween 80 0.5% 0.3-0.6% emulsi- fier (3) Water 79.5% 44.2-87.0% diluent 100.0% Heat (2) to 70°C. Heat (3) to 72°C. Add (3) to (2) with continuous agitation. When (3) and (2) cool to 40°C, add (1) with continuous agitation until room temperature is reached. L. PAINT 1. ENAMEL CHEMICAL % OF TOTAL RANGE ACTION Dihydrocarvone 1.00% 1-10% fungi¬ cide Titanium dioxide 14.91% 12-16% pigment Calcium carbonate 29.83% 25-35% pigment Silicate 4.81% 3-6% pigment Soya alkyd resin 25.72% 22-28% pigment (binder) Mineral spirits 23.73% 5-37% solvent 100.00% (thinner) LATEX CHEMICAL % OF TOTAL RANGE ACTION Limonen-10-ol 1.0% 1-10% fungi¬ cide Titanium dioxide 10.76% 8-12% pigment Silicate 12.91% 10-16% pigment Calcium carbonate 20.91% 15-25% pigment Vinyl acrylic resin solids 12.22% 10-16% vehicle (binder) Glycol 8.30% 6-10% solvent (thinner) Water 34.00% 12-50% solvent 100.00% (thinner) While only certain preferred embodiments of this invention have been shown and described by way of illustration, many modifications will occur to those skilled in the art and it is, therefore, desired that it be understood that it is intended herein, to cover all such modifications that fall within the true spirit and scope of this invention.

Claims: CLAIMS _ 33 _ 1. A method of killing fungi or yeast comprising treating fungi or yeast in their habitat with a lethal concentration of carveol, dihydrocarveol, dihydrocarvone, menth-l-en-9-ol, or limonen-10-ol. 2. A method of Claim 1 for killing yeast wherein said yeast is Candida. 3. A method of Claim 1 for killing fungi wherein said fungi are selected from a group consisting of Microsporum, Aureo¬ basidium, Cladosporium, and Phialophora. 4. A method of killing bacteria, fungi or yeast comprising treating bacteria, fungi or yeast in their habitat with a lethal concentration of menth-l-en-9-ol or limonen-10-ol. 5. A method of Claim 4 for killing bacteria wherein said bacteria are selected from a group consisting of Staphylo¬ coecus, Streptococcus, Escherichera, Salmonella, and Pseudo¬ monas. 6. A method of Claim 4 for killing fungi wherein said fungi are selected from a group consisting of Aureobasidiu and Cladosporium.

Inventors: CHASTAIN DOYLE E, SANDERS CHRISTINE C, SANDERS W EUGUEN JR, CHASTAIN, DOYLE, E., SANDERS, CHRISTINE, C., SANDERS, W., EUGUEN, JR.
Applicants: CHASTAIN DOYLE E, CHASTAIN, DOYLE, E.
Application year: 1994
Main classification: A01N31
IPC codes: A01N31, A01N35, A61K31, A61P31, C11D3